CN105742609A - Preparation method for spirogyra-based biomass carbon material/nanometer sulfur composite material - Google Patents
Preparation method for spirogyra-based biomass carbon material/nanometer sulfur composite material Download PDFInfo
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Abstract
The invention relates to a preparation method for a spirogyra-based biomass carbon material/nanometer sulfur composite material. The method comprises the following steps of washing and drying spirogyra, heating the washed and dried spirogyra in a vacuum tubular furnace, carrying out heat preservation and carbonization at 500-900 DEG C, mixing the carbonized spirogyra with nanometer sulfur with ultrasound, carrying out ball milling, drying the ball-milled mixture by an air blow drying box, heating the dried mixture in the vacuum tubular furnace, carrying out heat preservation for 3-6 hours at 100-200 DEG C, and afterwards cooling the mixture subjected to heat preservation to a room temperature with the furnace to obtain the target product, namely the spirogyra-based biomass carbon/nanometer sulfur composite material. According to the preparation method, the spirogyra is taken as a precursor for the first time, and a biomass carbon material with a continuous sheet-shaped structure similar to graphene and with nanoscale thickness is synthesized; the biomass carbon material comprises the sheet-shaped structure composed of continuous fibers, also is provided with nanoscale pores and is high in uniformity and continuity, the loading of sulfur particles is facilitated, and the obtained composite material has favorably electrochemical performance.
Description
Technical field
Technical scheme relates to biomass carbon/sulfur composite continuous based on water and preparation method thereof and application, belongs to lithium sulfur battery anode material field.
Background technology
Lithium-sulfur cell, due to plurality of advantages such as its specific energy are high, safety is good, obtains the extensive concern of many researchers.The theoretic specific capacity of lithium-sulfur cell is 1675mAh/g, and specific energy can reach 2600Wh/kg, and there are two voltage platforms, more superior than general performance of lithium ion battery, meets the current electronic product portable demand to battery " light, thin, little ".Additionally, sulfur reserves in nature are very abundant, price is relatively cheap, and sulfur is a kind of environmentally friendly element.Therefore, sulfur positive electrode is one of secondary power anode material of lithium battery with Development volue and application prospect.
But sulfur positive electrode there is also some problems: it is low that lithium-sulfur cell also exists positive electrode active material utilization, and cycle life is short, the problems such as high rate performance is poor, constrain its practical application.The reason causing these problems is in that: 1. the electron conduction of sulfur and product lithium sulfide and ionic conductivity are poor, causes that the utilization rate of active component is relatively low and high rate performance is poor；2. sulfur is easily soluble in organic electrolyte at the many lithium sulfides of intermediate product of charge and discharge process, causes capacity attenuation serious.
At present, domestic and international researcher sulfur-bearing anode composite material modified in conduct in-depth research and achieve huge progress, wherein sulfur/carbon composite is considered as the most potential lithium sulfur battery anode material.Material with carbon element, because having the preparation of good conductivity, environmental friendliness, various structures, multiple advantage the is used to sulfenyl composite such as specific surface area is big, adsorptivity is strong, is widely used improving lithium-sulfur cell aspect of performance.Therefore, research worker adopts certain complex method to be nested in by the sulfur of nano-grade size in gap micro-, mesoporous or the duct of material with carbon element, develop sulfur/carbon composite that a series of structure and morphology is different: the composites such as sulfur/mesoporous carbon, sulfur/microporous carbon, sulfur/carbon nano tube/graphene, present the battery performance of excellence simultaneously.Such as, CN104638246A reports Na2S2O3After solution mixes with reduced graphene dispersion liquid, ultrasonic disperse processes, and then adds hydrochloric acid solution under ultrasonic wave added, reacts final vacuum sucking filtration, cleaning, dries, and by filter membrane and the separating substances on filter membrane, obtains graphene-based flexible lithium sulfur battery anode material；The preparation method that CN104766967A discloses a kind of lithium-sulphur cell positive electrode sulfur/carbon composite, utilize carbon support material and the elemental sulfur compounds such as the white carbon black after low-kappa number, mesoporous carbon, CNT, Graphene, thus obtaining high performance sulfur/carbon composite.But what do not allow to avoid is that the synthesis technique of above-mentioned material with carbon element is more complicated, preparation cost is higher, though using the battery performance that itself and elemental sulfur carry out the positive electrode that compound prepares to get a promotion, but the advantage that lithium-sulfur cell system is with low cost is sacrificed, therefore, how not only to keep performance that material with carbon element is good but also be able to maintain that the technology of preparing of a lower cost, be research worker problem demanding prompt solution.
Meanwhile, biosystem is a huge resources bank, provide not only abundant raw material, and gives, in research and development new function structural material, the enlightenment that researcher is very big.Wherein, some agriculture and forestry organic waste materials can be used to prepare biomass carbon material, so both can effectively reduce the production cost of material with carbon element, it is achieved the sustainable development of material with carbon element, also opens up a new way for effectively utilizing of agriculture and forestry organic waste material simultaneously.Such as, CN104681800A discloses preparation method and the application of a kind of biological carbon based on corn straw/sulfur composite, adopts ZnCl2Pretreatment, KOH activation and the method such as heat treatment carbonization prepare biomass carbon material, and mix with the particular solution of sulfur and prepare sulfur carbon composite.Moreover, the pollutant such as agricultural, ocean can also as one of source of material with carbon element: in recent years owing to the mankind are to the irrational exploitation of natural resources, and the pollution of industrial and agricultural production, World Ecosystem environment there occurs obvious change, body eutrophication phenomenon is day by day serious, algae abnormality proliferation, interference fresh water and marine ecology balance, thus endangering human health.
Summary of the invention
It is an object of the invention to for the deficiency that material with carbon element is relatively costly in lithium-sulfur cell system existed in current techniques, design and the preparation method that a kind of water silk floss based biomass material with carbon element/nano-sulfur composite positive pole with low cost is provided, namely pass through wet ball grinding and in tube furnace, melt the modes such as heating, nano-sulfur is made to be dispersed in the middle of surface and the hole of water silk floss based biomass carbon, the electric conductivity and the captured sulfur result that make water silk floss based biomass material with carbon element can be not fully exerted in above-mentioned composite, ensure that the raising of water silk floss based biomass material with carbon element/nano-sulfur composite chemical property.Additionally, the bigger specific surface area of water silk floss based biomass material with carbon element is beneficial to the many lithium sulfides of intermediate product of absorption solubility, slow down effect of shuttling back and forth, improve the cycle performance of electrode.
The technical scheme is that
The preparation method of a kind of water silk floss based biomass material with carbon element/nano-sulfur composite, comprises the following steps:
(1) after water silk floss water directly being cleaned, again the water silk floss after cleaning is immersed in deionized water, ultrasonic cleaning 30～60 minutes, then deionized water is changed into ethanol ultrasonic cleaning 30～60 minutes again, with successively respectively in deionized water and ethanol ultrasonic cleaning be designated as cleaning once, clean 2～5 times, clarify to solution；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven at 60 DEG C dry 3～9 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected; after rising to 500～900 DEG C by the heating rate of 2～12 DEG C/min; insulation carbonization 1～4 hour, cools to room temperature afterwards with the furnace, obtains water silk floss based biomass material with carbon element；
(4) water silk floss based biomass material with carbon element nano-sulfur and upper step obtained is immersed in deionized water, ultrasonic mixing 30～60 minutes；Wherein, quality is than biomass carbon material: nano-sulfur=1:2～4；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 3～6 hours under the rotating speed of 300～900 revs/min；
(6) take out the mixed solution after ball milling in step 5 subsequently, be placed at air dry oven 60 DEG C～120 DEG C and be baked to, after 6～12 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 100 DEG C～200 DEG C by the heating rate of 2～12 DEG C/min and be incubated 3～6 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
The invention have the benefit that
It has been investigated that silk algae is a kind of common explosive hair algae, breeding is with adaptable, and is widespread in nature.So the present invention combines produced problem in research at present, adopt biological material as carbon source, namely continuous for presoma with water first, the continuous sheet structure being similar to Graphene and biomass carbon material that thickness is nanoscale are synthesized, the laminated structure that this biomass carbon material is made up of continuous fiber is constituted, and having again nanoscale hole, uniform continuity is better, is conducive to load nano-sulfur.After high-temperature heat treatment, nano-sulfur penetrates in the hole of carbon base body, forms sulfur carbon complex, thus reducing the loss of active substance.The present invention makes novel lithium battery positive electrode not only by the method for green syt, and can curb environmental pollution to a certain extent, realize refuse reclamation, reach the purpose of energy-saving and emission-reduction, make the research also have great learning value while commercially valuable.
In embodiment 1, as seen in figs. 6 and 7, under the multiplying power of 0.1C, its first discharge specific capacity, up to 1230mAh/g, remains to keep 821mAh/g after circulating 100, illustrates that prepared water silk floss base material with carbon element can promote that sulfur plays its effect.This should be owing to the size of nano-sulfur is little, be conducive to shortening ion the evolving path wherein, the transmission promoting electric charge and transfer, water silk floss base material with carbon element has the characteristics such as hole is abundant, specific surface area is high simultaneously, more nano-sulfur particles can be adsorbed, therefore, water silk floss base material with carbon element/nano-sulfur anode composite has higher discharge capacity.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) figure of water silk floss based biomass material with carbon element under different enlargement ratios in embodiment 1；Wherein, Fig. 1 a is 500 enlargement ratios, and Fig. 1 b is 2000 enlargement ratios, and Fig. 1 c is 10000 enlargement ratios, and Fig. 1 d is 50000 enlargement ratios；
Fig. 2 is scanning electron microscope (SEM) figure of water silk floss based biomass carbon/nano-sulfur composite under different enlargement ratios in embodiment 1；Wherein, Fig. 2 e is 5000 enlargement ratios, and Fig. 2 f is 50000 enlargement ratios；
Fig. 3 a is transmission electron microscope (TEM) figure of water silk floss based biomass material with carbon element in embodiment 1；Fig. 3 b is transmission electron microscope (TEM) figure of water silk floss based biomass carbon/nano-sulfur composite in embodiment 1；
Fig. 4 is atomic force microscope (AFM) figure of water silk floss based biomass carbon/nano-sulfur composite in embodiment 1；
Fig. 5 is X-ray diffraction (XRD) figure of nano-sulfur, the water silk floss based biomass material with carbon element of embodiment 1 preparation, water silk floss based biomass carbon/nano-sulfur composite；
Fig. 6 be in embodiment 1 water silk floss based biomass carbon/nano-sulfur composite as lithium-sulphur cell positive electrode cycle life curve under 0.1C；
Fig. 7 be in embodiment 1 water silk floss based biomass carbon/nano-sulfur composite as lithium-sulphur cell positive electrode charging and discharging curve under 0.1C；
Detailed description of the invention
Water silk floss of the present invention is wawter bloom phenomenon common in river course or water environment, is that a kind of filamentous alga is biological.Water silk floss in following example is specially in laboratory water vat and cultivates and obtain, but is not limited to this.
Embodiment 1
(1) water silk floss is cleaned up repeatedly, remove impurity, and it is continuous to put into addition deionized water immersion water in beaker, then ultrasonic cleaning 30 minutes, cleaning solvent is changed into ethanol ultrasonic cleaning 30 minutes more again, by above-mentioned cleaning process, three times repeatedly (i.e. water and ethanol ultrasonic cleaning in turn, namely washes once, and ethanol is washed once；Washing once, ethanol is washed once again；Washing once, ethanol is washed once again.Following example with) to solution clarify；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven at 60 DEG C dry 6 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected, after rising to 700 DEG C by the heating rate of 5 DEG C/min, insulation carbonization 2 hours, cool to room temperature afterwards with the furnace, obtain water silk floss based biomass material with carbon element；
(4) gauge water silk floss based biomass material with carbon element and the nano-sulfur (size≤50nm of nano sulfur solid are taken according to the ratio that biomass carbon material and nano-sulfur mass ratio are 1:2, following example are same), after adding a small amount of deionized water submergence, ultrasonic mixing 30 minutes；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 3 hours under the rotating speed of 600 revs/min；
(6) take out the mixed solution after ball milling in step 5 subsequently, be placed at air dry oven 60 DEG C and be baked to, after 10 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 150 DEG C by the heating rate of 5 DEG C/min and be incubated 3 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
(8) using prepared water silk floss based biomass carbon/nano-sulfur composite as active material, acetylene black is conductive agent, Kynoar is binding agent, and by water silk floss based biomass carbon/nano-sulfur composite: acetylene black: the weight ratio of Kynoar=8:1:1 is inserted mixing in mortar, ground uniformly, instill N-methyl pyrrolidinone solvent and be ground to pulpous state, slurry is uniformly applied on aluminium foil, put into dry 12h in the thermostatic drying chamber of 60 DEG C, re-use tablet machine at 5MPa pressure flakiness, thus prepare based lithium-ion battery positive plate；Prepared positive plate and metal lithium sheet are assembled CR2025 button cell in the glove box of full argon.
Prepared sample carries out SEM (FEI Co. of the U.S. produces for SEM, NovaNanoSEM450) analyze.Fig. 1 is the SEM figure of the water silk floss base material with carbon element after 700 DEG C of high temperature cabonizations that embodiment 1 is obtained, as it can be seen, the laminated structure that this biomass carbon material is made up of continuous fiber is constituted, and have nanoscale hole, be conducive to sulfur loaded granule, thus reducing the loss of active substance.Fig. 2 is the SEM figure of the obtained water silk floss based biomass carbon/nano-sulfur composite of embodiment 1, as it can be seen, nano-sulfur penetrates in the hole of carbon base body after high-temperature heat treatment, thus forming sulfur carbon complex.
Prepared sample carries out TEM (NEC Optical Co., Ltd produces for TEM, JEM-2100F) analyze.Fig. 3 a is the TEM figure of water silk floss based biomass material with carbon element in embodiment 1；Fig. 3 b is the TEM figure of water silk floss based biomass carbon/nano-sulfur composite in embodiment 1.As shown in Figure 3, after water silk floss based biomass material with carbon element and sulfur compound, lamellar spacing substantially strengthens.
Prepared sample is carried out AFM (Agilent, 5500, Agilent company of the U.S. produce) analyze.Fig. 4 is the AFM figure of water silk floss based biomass carbon/nano-sulfur composite in embodiment 1.As shown in Figure 4, from the 3D effect figure after water silk floss based biomass material with carbon element and nano-sulfur compound, the thickness of water silk floss based biomass carbon/nano-sulfur composite is approximately in about 10nm.
Prepared sample carries out XRD (Rigaku company produces for XRD, smartLab) analyze.Fig. 5 is the XRD figure of nano-sulfur, the water silk floss based biomass material with carbon element of embodiment 1 preparation, water silk floss based biomass carbon/nano-sulfur composite.As shown in Figure 5, nano-sulfur through with water silk floss based biomass material with carbon element compound after, Partial Feature peak disappears in sulfur carbon composite, illustrates that nano-sulfur is scattered in biomass carbon material uniformly.
Prepared sample is carried out chemical property analysis (BTS-5V5mA, new prestige).Fig. 6 be in embodiment 1 water silk floss based biomass carbon/nano-sulfur composite as lithium-sulphur cell positive electrode cycle life curve under 0.1C, as shown in the figure, under the multiplying power of 0.1C, its first discharge capacity up to 1230mAh/g, and 100 circulation after discharge capacity still can keep 821mAh/g.
Prepared sample is carried out chemical property analysis (BTS-5V5mA, new prestige).Fig. 7 be in embodiment 1 water silk floss based biomass carbon/nano-sulfur composite as lithium-sulphur cell positive electrode charging and discharging curve under 0.1C, as shown in the figure, under the multiplying power of 0.1C, water silk floss based biomass carbon/nano-sulfur composite shows obvious discharge platform at about 2.1V.
Embodiment 2
The preparation method being applied to the water silk floss based biomass carbon/nano-sulfur composite of lithium-sulfur cell, step, with embodiment 1, is a difference in that, the diamond heating in step (3) is to 500 DEG C.
(1) water silk floss is cleaned up repeatedly, remove impurity, and put into that to add deionized water immersion water in beaker continuous, then ultrasonic cleaning 30 minutes, then cleaning solvent is changed into ethanol ultrasonic cleaning 30 minutes again, by above-mentioned cleaning process three times repeatedly, clarify to solution；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven at 60 DEG C dry 6 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected, after rising to 500 DEG C by the heating rate of 5 DEG C/min, insulation carbonization 2 hours, cool to room temperature afterwards with the furnace, obtain water silk floss based biomass material with carbon element；
(4) gauge water silk floss based biomass material with carbon element and nano-sulfur are taken according to the ratio that biomass carbon material and nano-sulfur mass ratio are 1:2, after adding a small amount of deionized water submergence, ultrasonic mixing 30 minutes；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 3 hours under the rotating speed of 600 revs/min；
(6) take out the mixed solution after ball milling in step 5 subsequently, be placed at air dry oven 60 DEG C and be baked to, after 10 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 150 DEG C by the heating rate of 5 DEG C/min and be incubated 3 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
(8) using prepared water silk floss based biomass carbon/nano-sulfur composite as active material, acetylene black is conductive agent, Kynoar is binding agent, and by water silk floss based biomass carbon/nano-sulfur composite: acetylene black: the weight ratio of Kynoar=8:1:1 is inserted mixing in mortar, ground uniformly, instill N-methyl pyrrolidinone solvent and be ground to pulpous state, slurry is uniformly applied on aluminium foil, put into dry 12h in the thermostatic drying chamber of 60 DEG C, re-use tablet machine at 5MPa pressure flakiness, thus prepare based lithium-ion battery positive plate；Prepared positive plate and metal lithium sheet are assembled CR2025 button cell in the glove box of full argon.
The characterization result of material and electrochemical performance data and embodiment 1 are similar to.
Embodiment 3
The preparation method being applied to the water silk floss based biomass carbon/nano-sulfur composite of lithium-sulfur cell, step, with embodiment 1, is a difference in that, the diamond heating in step (3) is to 900 DEG C.
(1) water silk floss is cleaned up repeatedly, remove impurity, and put into that to add deionized water immersion water in beaker continuous, then ultrasonic cleaning 30 minutes, then cleaning solvent is changed into ethanol ultrasonic cleaning 30 minutes again, by above-mentioned cleaning process three times repeatedly, clarify to solution；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven at 60 DEG C dry 6 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected, after rising to 900 DEG C by the heating rate of 5 DEG C/min, insulation carbonization 2 hours, cool to room temperature afterwards with the furnace, obtain water silk floss based biomass material with carbon element；
(4) gauge water silk floss based biomass material with carbon element and nano-sulfur are taken according to the ratio that biomass carbon material and nano-sulfur mass ratio are 1:2, after adding a small amount of deionized water submergence, ultrasonic mixing 30 minutes；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 3 hours under the rotating speed of 600 revs/min；
(6) take out the mixed solution after ball milling in step 5 subsequently, be placed at air dry oven 60 DEG C and be baked to, after 10 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 150 DEG C by the heating rate of 5 DEG C/min and be incubated 3 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
(8) using prepared water silk floss based biomass carbon/nano-sulfur composite as active material, acetylene black is conductive agent, Kynoar is binding agent, and by water silk floss based biomass carbon/nano-sulfur composite: acetylene black: the weight ratio of Kynoar=8:1:1 is inserted mixing in mortar, ground uniformly, instill N-methyl pyrrolidinone solvent and be ground to pulpous state, slurry is uniformly applied on aluminium foil, put into dry 12h in the thermostatic drying chamber of 60 DEG C, re-use tablet machine at 5MPa pressure flakiness, thus prepare based lithium-ion battery positive plate；Prepared positive plate and metal lithium sheet are assembled CR2025 button cell in the glove box of full argon.
The characterization result of material and electrochemical performance data and embodiment 1 are similar to.
Embodiment 4
The preparation method being applied to the water silk floss based biomass carbon/nano-sulfur composite of lithium-sulfur cell, step, with embodiment 1, is a difference in that, in step (5), ball milling is 5 hours.
(1) water silk floss is cleaned up repeatedly, remove impurity, and put into that to add deionized water immersion water in beaker continuous, then ultrasonic cleaning 30 minutes, then cleaning solvent is changed into ethanol ultrasonic cleaning 30 minutes again, by above-mentioned cleaning process three times repeatedly, clarify to solution；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven at 60 DEG C dry 6 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected, after rising to 700 DEG C by the heating rate of 5 DEG C/min, insulation carbonization 2 hours, cool to room temperature afterwards with the furnace, obtain water silk floss based biomass material with carbon element；
(4) gauge water silk floss based biomass material with carbon element and nano-sulfur are taken according to the ratio that biomass carbon material and nano-sulfur mass ratio are 1:2, after adding a small amount of deionized water submergence, ultrasonic mixing 30 minutes；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 5 hours under the rotating speed of 600 revs/min；
(6) take out the mixed solution after ball milling in step 5 subsequently, be placed at air dry oven 60 DEG C and be baked to, after 10 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 150 DEG C by the heating rate of 5 DEG C/min and be incubated 3 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
(8) using prepared water silk floss based biomass carbon/nano-sulfur composite as active material, acetylene black is conductive agent, Kynoar is binding agent, and by water silk floss based biomass carbon/nano-sulfur composite: acetylene black: the weight ratio of Kynoar=8:1:1 is inserted mixing in mortar, ground uniformly, instill N-methyl pyrrolidinone solvent and be ground to pulpous state, slurry is uniformly applied on aluminium foil, put into dry 12h in the thermostatic drying chamber of 60 DEG C, re-use tablet machine at 5MPa pressure flakiness, thus prepare based lithium-ion battery positive plate；Prepared positive plate and metal lithium sheet are assembled CR2025 button cell in the glove box of full argon.
The characterization result of material and electrochemical performance data and embodiment 1 are similar to.
Embodiment 5
The preparation method being applied to the water silk floss based biomass carbon/nano-sulfur composite of lithium-sulfur cell, step, with embodiment 1, is a difference in that, step (3) insulation carbonization 4 hours.
(1) water silk floss is cleaned up repeatedly, remove impurity, and put into that to add deionized water immersion water in beaker continuous, then ultrasonic cleaning 30 minutes, then cleaning solvent is changed into ethanol ultrasonic cleaning 30 minutes again, by above-mentioned cleaning process three times repeatedly, clarify to solution；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven at 60 DEG C dry 6 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected, after rising to 700 DEG C by the heating rate of 5 DEG C/min, insulation carbonization 4 hours, cool to room temperature afterwards with the furnace, obtain water silk floss based biomass material with carbon element；
(4) gauge water silk floss based biomass material with carbon element and nano-sulfur are taken according to the ratio that biomass carbon material and nano-sulfur mass ratio are 1:2, after adding a small amount of deionized water submergence, ultrasonic mixing 30 minutes；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 3 hours under the rotating speed of 600 revs/min；
(6) take out the mixed solution after ball milling in step 5 subsequently, be placed at air dry oven 60 DEG C and be baked to, after 10 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 150 DEG C by the heating rate of 5 DEG C/min and be incubated 3 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
(8) using prepared water silk floss based biomass carbon/nano-sulfur composite as active material, acetylene black is conductive agent, Kynoar is binding agent, and by water silk floss based biomass carbon/nano-sulfur composite: acetylene black: the weight ratio of Kynoar=8:1:1 is inserted mixing in mortar, ground uniformly, instill N-methyl pyrrolidinone solvent and be ground to pulpous state, slurry is uniformly applied on aluminium foil, put into dry 12h in the thermostatic drying chamber of 60 DEG C, re-use tablet machine at 5MPa pressure flakiness, thus prepare based lithium-ion battery positive plate；Prepared positive plate and metal lithium sheet are assembled CR2025 button cell in the glove box of full argon.
The characterization result of material and electrochemical performance data and embodiment 1 are similar to.
In sum, the substantive distinguishing features of the present invention is the preparation method providing a kind of novel biomass material with carbon element, the method is continuous for presoma with water, after certain processing carbonization treatment, make that hole is good, specific surface area is relatively big, the biomass carbon material of good adsorption performance, and above-mentioned material with carbon element and sulfur are carried out Application of composite in lithium-sulfur cell system.The method not only technical process is simple, with low cost, and can solve the nonconducting problem of sulfur positive pole, improves lithium-sulfur cell high rate performance, improves lithium-sulfur cell energy density and cycle-index so that it is first discharge specific capacity reaches 1230mAh/g.Use water silk floss based biomass material with carbon element to be possible not only to make novel lithium battery positive electrode, promote the combination property of battery, and can curb environmental pollution to a certain extent, turn waste into wealth, save the energy.
The preparation method of above-mentioned water silk floss based biomass material with carbon element/nano-sulfur composite positive pole, wherein involved raw material, equipment and technique are all known by those skilled in the art.
Unaccomplished matter of the present invention is known technology.
Claims (1)
1. a preparation method for water silk floss based biomass material with carbon element/nano-sulfur composite, is characterized by comprise the following steps:
(1) after water silk floss water directly being cleaned, again the water silk floss after cleaning is immersed in deionized water, ultrasonic cleaning 30 ~ 60 minutes, then deionized water is changed into ethanol ultrasonic cleaning 30 ~ 60 minutes again, with successively respectively in deionized water and ethanol ultrasonic cleaning be designated as cleaning once, clean 2 ~ 5 times, clarify to solution；
(2) the water silk floss cleaned up in step 1 is placed in vacuum drying oven under 60 ° of C dry 3 ~ 9 hours；
(3) heated continuous for water dry in step 2 by vacuum tube furnace under argon gas atmosphere is protected, after rising to 500 ~ 900 ° of C by the heating rate of 2～12 ° of C/min, insulation carbonization 1 ~ 4 hour, cool to room temperature afterwards with the furnace, obtain water silk floss based biomass material with carbon element；
(4) water silk floss based biomass material with carbon element nano-sulfur and upper step obtained is immersed in deionized water, ultrasonic mixing 30 ~ 60 minutes；Wherein, quality is than biomass carbon material: nano-sulfur=1:2 ~ 4；
(5) material aqueous solution that step 4 is obtained uses planetary ball mill wet ball grinding 3 ~ 6 hours under the rotating speed of 300 ~ 900 revs/min；
(6) take out the mixed solution after step 5 ball milling subsequently, be placed under 60 ° of C ~ 120 ° C of air dry oven and be baked to, after 6 ~ 12 hours, obtain the sulfur carbon complex solid powder dried；
(7) sulfur carbon complex solid powder step 6 obtained is heated by vacuum tube furnace under argon gas atmosphere is protected; rise to 100 ° of C ~ 200 ° C by the heating rate of 2～12 ° of C/min and be incubated 3 ~ 6 hours; cool to room temperature afterwards with the furnace, obtain target product water silk floss based biomass material with carbon element/nano-sulfur composite.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532012A (en) * | 2016-12-23 | 2017-03-22 | 浙江大学 | Sulfur-biomass carbon/transition metal composite electrode material and preparation method and application thereof |
| CN107473215A (en) * | 2017-07-31 | 2017-12-15 | 西安理工大学 | The preparation method of biomass porous carbon and carbon sulphur composite based on banana skin |
| CN107492644A (en) * | 2017-07-31 | 2017-12-19 | 西安理工大学 | The preparation method of biomass porous carbon and carbon sulphur composite based on corncob |
| CN107689446A (en) * | 2017-07-31 | 2018-02-13 | 西安理工大学 | The preparation method of biomass porous carbon and carbon sulphur composite based on catkin |
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| CN109830697A (en) * | 2019-01-24 | 2019-05-31 | 江苏大学 | A kind of preparation and its application of water silk floss porous three-dimensional electrode |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050679A (en) * | 2012-12-26 | 2013-04-17 | 浙江工业大学 | Spherical hollow porous MnO/C composite material and application thereof |
| CN103236560A (en) * | 2013-04-16 | 2013-08-07 | 浙江大学 | Lithium-sulfur battery sulfur/carbon composite positive electrode material, preparation method and applications thereof |
-
2016
- 2016-04-22 CN CN201610260212.2A patent/CN105742609B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050679A (en) * | 2012-12-26 | 2013-04-17 | 浙江工业大学 | Spherical hollow porous MnO/C composite material and application thereof |
| CN103236560A (en) * | 2013-04-16 | 2013-08-07 | 浙江大学 | Lithium-sulfur battery sulfur/carbon composite positive electrode material, preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIFENG WANG等: "Biotemplated MnO/C microtubes from spirogyra with improved electrochemical performance for lithium-ion batterys", 《ELECTROCHIMICA ACTA》 * |
| YONGGUANG ZHANG等: "Effect of mesoporous carbon microtube prepared by carbonizing the poplar catkin on sulfur cathode performance in Li/S batteries", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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